JP7034787B2 - Toner binder and toner - Google Patents

Description

The present invention relates to a toner binder and a toner used for developing an electrostatic charge image or a magnetic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

In recent years, there has been a strong demand for improving the low-temperature fixing property of toner from the viewpoint of energy saving of reducing energy consumption in the fixing process as well as promoting miniaturization, high speed, and high image quality of electrophotographic equipment.
As a means for lowering the fixing temperature of the toner, a technique for lowering the glass transition point of the binder resin is generally used.
However, if the glass transition point is set too low, powder agglutination (blocking) is likely to occur, so that the toner storage stability is deteriorated and the agglutination occurs in the developing tank, resulting in deterioration of image quality. There are challenges. Therefore, there is a limit to low-temperature fixing by a method of lowering the glass transition point.

Among them, a toner using crystalline polyester has been proposed as a toner composition containing a polyester-based toner binder having excellent low-temperature fixability and hot offset resistance. (Patent Documents 1 and 2)
By using the amorphous resin and the crystalline resin together as the binder resin, the low temperature fixability and glossiness of the toner are improved due to the melting characteristics of the crystalline resin.
However, if the content of the crystalline resin is increased, the resin strength may decrease, and the crystalline resin is amorphous due to the compatibilization of the crystalline resin and the binder resin during melt-kneading, resulting in glass transition of the toner. As the points decrease, the same problems as described above occur.

On the other hand, a method of reproducing the crystallinity of the crystalline resin by heat treatment after the melt-kneading step (Patent Document 3), a method of changing the monomer component used (Patent Documents 4 and 5), and the like have been proposed.
Although the low-temperature fixability and glossiness of the toner can be ensured by such a method, the hot offset resistance, the fluidity of the toner, and the heat-resistant storage stability which is the stability at high temperature storage are insufficient, and the charge stability and pulverization are performed. There is also a problem that the pulverizability at the time is lowered.
A method of coating with a shell layer obtained by a melt-suspension method or an emulsification / aggregation method has also been proposed (Patent Documents 6 to 9), but the crystalline resin is compatible with the binding resin of the core and is short. Since the reprecipitation of crystals is insufficient in time, the image strength and bending resistance after fixing are still insufficient.

Japanese Unexamined Patent Publication No. 2005-77930 Japanese Unexamined Patent Publication No. 2012-98719 Japanese Unexamined Patent Publication No. 2005-30995 Japanese Unexamined Patent Publication No. 2012-8371 JP-A-2007-292816 Japanese Unexamined Patent Publication No. 2011-197193 Japanese Unexamined Patent Publication No. 2011-197192 Japanese Unexamined Patent Publication No. 2011-186053 Japanese Unexamined Patent Publication No. 2006-251564

INDUSTRIAL APPLICABILITY The present invention has excellent toner fluidity, heat storage stability, charge stability, crushability, image strength, bending resistance, and document offset resistance while achieving both low-temperature fixability, glossiness, and hot offset resistance. It is an object of the present invention to provide a binder and a toner.

The present inventors have arrived at the present invention as a result of diligent studies to solve these problems.
That is, the present invention is the following two inventions.
(1) A toner binder containing a crystalline resin (A) which is a polycondensate of an alcohol component (x) and a carboxylic acid component (y), wherein the alcohol component (x) has 2 to 12 carbon atoms. It contains at least two types of chain or branched aliphatic diols (x1), and has the molar mass of the component (x1a) having the largest number of moles in (x1) and one of the components other than (x1a) (x1b). The difference in molar mass is less than 15 in at least one combination with the molar mass of (x1), and the total content of the components (x1b) other than (x1a) in (x1) is the terminal encapsulant (a2). It is 0.05 to 3 mol% based on the total number of moles of the alcohol component (x) excluding, and is in the range of 40 ° C to 100 ° C when the temperature is raised from 30 ° C to 10 ° C / min. A toner binder having at least one heat absorbing peak top in the chart by (DSC).
(2) Toner containing the above-mentioned toner binder and colorant.

According to the present invention, a toner having excellent low temperature fixability, glossiness and hot offset resistance, and excellent toner fluidity, heat storage stability, charge stability, crushability, image strength, bending resistance and document offset resistance. It has become possible to provide binders and toners.

Hereinafter, the present invention will be described in detail.
The toner binder of the present invention is a toner binder containing a crystalline resin (A) which is a polycondensate of an alcohol component (x) and a carboxylic acid component (y), and the alcohol component (x) has 2 carbon atoms. It contains at least two kinds of linear or branched aliphatic diols (x1) of ~ 12, and any one of the molar mass of the component (x1a) having the largest number of moles in (x1) and the component other than (x1a). The difference in molar mass is less than 15 in at least one combination of the two components (x1b) with the molar mass, and is in the range of 40 ° C. to 100 ° C. when the temperature is raised from 30 ° C. to 10 ° C./min. It is a toner binder having at least one endothermic peak top in the chart by a differential scanning calorimeter (DSC).

The toner binder of the present invention contains the crystalline resin (A) as an essential component. Then, as will be described in detail later, when the toner binder of the present invention is heated at a temperature of 30 ° C. to 10 ° C./min and measured by a differential scanning calorimeter (DSC), an endothermic peak is shown. It is a toner binder characterized by having at least one temperature (Tp) indicating the endothermic peak top in the range of 40 to 100 ° C.

The crystalline resin (A) used in the present invention is not particularly limited as long as it exhibits crystallinity and the Tp of (A) is in the range of 40 to 100 ° C.
The term "crystallinity" in the present invention refers to a resin having a maximum DSC curve and a clear endothermic peak in the first heating process of the DSC measurement described above.

The temperature (Tp) indicating the endothermic peak top of the toner binder in the present invention is 40 to 100 ° C, preferably 45 to 95 ° C, and more preferably 50 to 90 ° C. If Tp is less than 40 ° C, the fluidity, heat storage property, crushability, image strength after fixing, bending resistance and document offset property of the toner deteriorate, and if it exceeds 100 ° C, the low temperature fixing property and glossiness deteriorate. do. The endothermic peak top of the toner binder is preferably an endothermic peak top derived from the crystalline resin (A).
The temperature indicating the endothermic peak top refers to the temperature at the deepest part of the recess of the endothermic peak.
When there are two or more endothermic peaks, the temperature indicating the endothermic peak top of at least one endothermic peak may be in this range.

The crystalline resin (A) is a linear or branched aliphatic diol having an alcohol component (x) and a carboxylic acid component (y) as constituent raw materials, and the alcohol component (x) has an alkyl group having 2 to 12 carbon atoms. At least one combination of the molar mass of the component (x1a) having the largest molar number in (x1) and the molar mass of the component (x1b) other than (x1a) containing at least two kinds of x1). As long as the difference in molar mass is less than 15, the chemical structure is not particularly limited.
Examples of the crystalline resin (A) include crystalline polyester (a11), crystalline polyurethane (a12), crystalline polyurea (a13), crystalline polyamide (a14), crystalline polyvinyl (a15) and the like. Of these, those having at least one group selected from the group consisting of an ester group, a urethane group, a urea group, an amide group, an epoxy group and a vinyl group are preferable, and an alcohol component (x) and a carboxylic acid component (y) are preferable. ) Is more preferable, because of the ease of introduction of the crystalline polyester (a11). Further, two or more kinds of these crystalline resins may be used in combination.

A more preferable crystalline polyester (a11) is a polyester resin obtained by reacting the alcohol component (x) with the carboxylic acid component (y).

As the alcohol component (x), a linear or branched aliphatic diol component (x1) having 2 to 12 carbon atoms, which is an essential component, a diol component (x2) other than (x1), and an alcohol component having a trivalent or higher valence (x1), if necessary, (x). x3) can be mentioned.

Examples of the linear or branched aliphatic diol component (x1) having 2 to 12 carbon atoms include a linear aliphatic diol component having 2 to 12 carbon atoms and a branched aliphatic diol component having 2 to 12 carbon atoms.
The linear aliphatic diol component includes ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8. -Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol and the like can be mentioned.
Examples of the branched aliphatic diol component include 2-methyl-1,4-butanediol and 2-methyl-1,8-octanediol.
Of these, (x1) is preferably a linear aliphatic diol component having 2 to 12 carbon atoms, and more preferably ethylene glycol, 1,3-, from the viewpoint of crystallinity and compatibility with the amorphous resin. Propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and particularly preferably 1,6-hexanediol. They are 1,9-nonanediol and 1,10-decanediol. Two or more of these may be used in combination, but one is preferable from the viewpoint of low temperature fixability.
Note that (x1) does not contain an alicyclic diol.

Examples of the diol component (x2) other than (x1) include alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.) and 4 carbon atoms. ~ 36 alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), alkylene oxides of the above alicyclic diols (hereinafter, “alkylene oxide” is abbreviated as AO) [ethylene oxide (hereinafter, abbreviated as AO) [ethylene oxide (hereinafter, abbreviated as AO). "Ethethylene oxide" is abbreviated as EO), propylene oxide (hereinafter, "propylene oxide" is abbreviated as PO), butylene oxide (hereinafter, "butylene oxide" is abbreviated as BO), etc.] Additives (number of added moles) 1 to 30), AO (EO, PO, BO, etc.) adducts (additional moles 2 to 30) of bisphenol compounds (bisphenol A, bisphenol F, bisphenol S, etc.), polylactone diols (polyε-caprolactone diol, etc.) And polybutadiene diol and the like. Two or more of these may be used in combination.

If necessary, the trihydric or higher alcohol component (x3) used in combination with the diol component (x1) to (x2) is a trivalent or higher-valent polyol, specifically, a trivalent or higher-valent polyol. Can be mentioned.
If necessary, the 3- to 8-valent or higher valence polyol used in combination with the diol component (x1) includes a 3- to 8-valent or higher valent polyhydric aliphatic alcohol (alcan) having 3 to 36 carbon atoms. Polyols and their intramolecular or intermolecular dehydrations such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin; saccharides and derivatives thereof such as sucrose and methylglucoside); trisphenol compounds. AO adduct (additional moles 2 to 30) of (trisphenol PA, etc.); AO adduct (additional moles 2 to 30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [hydroxyethyl (meth) Copolymers of acrylate and other vinyl monomers, etc.]; etc.
Of these, preferred are AO adducts of trihydric aliphatic alcohols and novolak resins having a valence of 3 to 8 or more, and more preferred are AO adducts of novolak resin.

The crystalline polyester (a11) is selected from the group consisting of a carboxylic acid (salt) group, a sulfonic acid (salt) group, a sulfamic acid (salt) group and a phosphate (salt) group in addition to the diol component (x1). A diol (x1') having at least one group may be used as a constituent unit.
By using a diol (x1') having these functional groups as a constituent unit, the chargeability of the toner and the heat-resistant storage stability are improved.
The "acid (salt)" in the present invention means an acid or a salt salt.
A polyester resin obtained by reacting a diol component (x1), a diol having a functional group (x1'), and a carboxylic acid component (y) as raw materials is preferable as the crystalline polyester (a11). As the diol having a functional group (x1'), only one kind may be used, or two or more kinds may be used in combination.

Examples of the diol (x1') having a carboxylic acid (salt) group include tartaric acid (salt), 2,2-bis (hydroxymethyl) propanoic acid (salt), and 2,2-bis (hydroxymethyl) butanoic acid (salt). And 3- [bis (2-hydroxyethyl) amino] propanoic acid (salt) and the like.

Examples of the diol (x1') having a sulfonic acid (salt) group include 2,2-bis (hydroxymethyl) ethanesulfonic acid (salt) and 2- [bis (2-hydroxyethyl) amino] ethanesulfonic acid (salt). And 5-sulfo-isophthalic acid-1,3-bis (2-hydroxyethyl) ester (salt) and the like.

Examples of the diol (x1') having a sulfamic acid (salt) group include N, N-bis (2-hydroxyethyl) sulfamic acid (salt), N, N-bis (3-hydroxypropyl) sulfamic acid (salt), and the like. Examples thereof include N, N-bis (4-hydroxybutyl) sulfamic acid (salt) and N, N-bis (2-hydroxypropyl) sulfamic acid (salt).

Examples of the diol (x1') having a phosphoric acid (salt) group include bis (2-hydroxyethyl) phosphate (salt).
The salts constituting the acid salt include ammonium salts and amine salts (methylamine salt, dimethylamine salt, trimethylamine salt, ethylamine salt, diethylamine salt, triethylamine salt, propylamine salt, dipropylamine salt, tripropylamine salt, butylamine). Salts, dibutylamine salts, tributylamine salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, N-methylethanolamine salts, N-ethylethanolamine salts, N, N-dimethylethanolamine salts, N, N- Diethylethanolamine salt, hydroxylamine salt, N, N-diethylhydroxylamine salt, morpholin salt, etc.), quaternary ammonium salt [tetramethylammonium salt, tetraethylammonium salt, trimethyl (2-hydroxyethyl) ammonium salt, etc.], alkali Examples include metal salts (sodium salt, potassium salt, etc.).

Among the functional group-bearing diols (x1'), those having a carboxylic acid (salt) group-bearing diol (x1') and a sulfonic acid (salt) group are preferable from the viewpoint of toner chargeability and heat-resistant storage stability. It is a diol (x1').

The alcohol component (x) of the present invention contains at least two types of linear or branched aliphatic diols (x1) having 2 to 12 carbon atoms, and the molar of the component (x1a) having the largest molar number among (x1). The difference in molar mass is less than 15 in at least one combination of the mass and the molar mass of the component (x1b) other than (x1a). If this condition is not satisfied, the low temperature fixability, hot offset resistance and storage stability when used for toner will be poor.

The content of the component (x1a) having the largest number of moles in the alcohol component (x) constituting the crystalline resin (A) is the total mole of the alcohol component (x) from the viewpoint of low temperature fixability and hot offset resistance. Based on the number, it is preferably 70 to 99.99 mol%, more preferably 70 to 99.95 mol%, particularly preferably 90 to 99.95 mol%, and most preferably 97 to 99.95 mol%.

The total content of the component (x1b) other than (x1a) is preferably 0.01 to 3 based on the total number of moles of the alcohol component (x) from the viewpoint of low temperature fixability, hot offset resistance and heat storage resistance. It is mol%, more preferably 0.05 to 3 mol%, and most preferably 0.05 to 1 mol%.
The component (x1b) other than (x1a) may be one type or two or more types.

When the alcohol component (x) contains a diol component (x2) other than (x1) and a trihydric or higher alcohol component (x3), the total content of (x2) and (x3) is preferably 29.5. It is mol% or less, more preferably 9.5 mol% or less, and most preferably 2.5 mol% or less.

The carboxylic acid component (y) is preferably composed of a dicarboxylic acid (y1) and, if necessary, a trivalent or higher valent polycarboxylic acid (y2).

Examples of the dicarboxylic acid (y1) include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
Examples of the aliphatic dicarboxylic acid include dodecanecarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, and dodecanedioic acid, octadecanedicarboxylic acids, which have 2 to 50 carbon atoms (including carbon of the carbonyl group). Decyl succinic acid, etc.); Alkendicarboxylic acid having 4 to 50 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, etc.); Examples thereof include 6 to 40 alicyclic dicarboxylic acids [dimeric acid (dimerized linoleic acid) and the like].
Examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid and the like. ) Etc. can be mentioned. Two or more of these may be used in combination.

Examples of the trivalent or higher carboxylic acid component (y2) include polycarboxylic acids having a valence of 3 to 6 or more. Examples of the polycarboxylic acid having a valence of 3 to 6 or more are an aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.) and an aliphatic tricarboxylic acid having 6 to 36 carbon atoms. (Hexantricarboxylic acid, etc.), Vinyl polymer of unsaturated carboxylic acid [number average molecular weight (Mn): 450 to 10,000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, and styrene / fumal Acid copolymers, etc.) and the like. The number average molecular weight (Mn) is determined by gel permeation chromatography (GPC).

Among these carboxylic acids, from the viewpoint of crystallinity, an aliphatic dicarboxylic acid is preferable, an aliphatic dicarboxylic acid having 2 to 50 carbon atoms is more preferable, and an aliphatic dicarboxylic acid having 4 to 12 carbon atoms is particularly preferable. It is an acid, most preferably adipic acid, sebacic acid, or dodecanedioic acid.
When a copolymerized aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, t-butylisophthalic acid, and lower alkyl esters thereof) is used, the copolymerization amount of the aromatic dicarboxylic acid is 20 mol% or less. preferable.

As the dicarboxylic acid or the trivalent or higher valent polycarboxylic acid, the acid anhydrides described above or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) may be used.

Crystalline polyurethane (a12)
Examples of the crystalline polyurethane (a12) include a heavy adduct of the crystalline polyester (a11) and the diisocyanate (v2), the crystalline polyester (a11), the alcohol component (x), and the diisocyanate (v2). Examples include heavy adducts of.
The crystalline polyurethane (a12) as a heavy adduct of the crystalline polyester (a11) and the diisocyanate (v2) can be obtained by reacting the crystalline polyester (a11) with the diisocyanate (v2). The crystalline polyurethane (a12) as a heavy adduct of the crystalline polyester (a11), the diol components (x1) to (x3) and the diisocyanate (v2) is the crystalline polyester (a11) and the diol components (x1) to (x1). It can be obtained by reacting x3) with diisocyanate (v2).

Further, by using the diol having a functional group (x1') as a constituent unit in addition to the diol components (x1) to (x3), the chargeability of the toner and the heat-resistant storage stability are improved.

The diisocyanate (v2) includes aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same applies hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, and modified products of these diisocyanates (urethane groups, etc.). Carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product, etc.) and a mixture of two or more thereof can be mentioned.

Examples of the aromatic diisocyanate having 6 to 20 carbon atoms include 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, m- or p-xylylene diisocyanate. Isocyanate (XDI), α, α, α', α'-tetramethylxylylene diisocyanate (TMXDI), 2,4'-or 4,4'-diphenylmethane diisocyanate (MDI), crude diaminophenylmethane diisocyanate (crude MDI) And so on.

Examples of the aliphatic diisocyanate having 2 to 18 carbon atoms include a chain aliphatic diisocyanate having 2 to 18 carbon atoms and a cyclic aliphatic diisocyanate having 3 to 18 carbon atoms.
Examples of the chain aliphatic diisocyanate having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-. Diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and mixtures thereof. Will be.

Examples of the cyclic aliphatic diisocyanate having 3 to 18 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (isocyanate). 2-Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornan diisocyanate and mixtures thereof can be mentioned.

The modified product of diisocyanate contains at least one group selected from the group consisting of urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group. Etc. are used, such as modified MDI (urethane-modified MDI, carbodiimide-modified MDI and trihydrocarbodiimide-modified MDI, etc.), urethane-modified TDI and a mixture thereof [for example, a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)] and the like. Can be mentioned.

Of these diisocyanates (v2), aromatic diisocyanates having 6 to 15 carbon atoms and aliphatic diisocyanates having 4 to 15 carbon atoms are preferable, and TDI, MDI, HDI, hydrogenated MDI and IPDI are more preferable. Is.

Crystalline polyurea (a13)
Examples of the crystalline polyurea (a13) include a heavy adduct of the crystalline polyester (a11), a diamine (z) and a diisocyanate (v2). Such crystalline polyurea (a13) can be obtained by reacting crystalline polyester (a11) with diamine (z) and diisocyanate (v2).

Examples of the diamine (z) include aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms.
Examples of the aliphatic diamine having 2 to 18 carbon atoms include chain aliphatic diamines and cyclic aliphatic diamines.

Examples of chain aliphatic diamines include alkylenediamines having 2 to 12 carbon atoms (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and polyalkylene (2 to 6 carbon atoms) polyamines [diethylenetriamine, imino. Bispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.] and the like can be mentioned.
Examples of the cyclic aliphatic polyamine include alicyclic diamines having 4 to 15 carbon atoms {1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline) and 3 , 9-Bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.} and heterocyclic diamines with 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1,4-Diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc.] and the like.

The aromatic diamine having 6 to 20 carbon atoms includes an unsubstituted aromatic diamine and an alkyl group having an alkyl group (an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n- or an isopropyl group and a butyl group). Examples include diamine.

Examples of the unsubstituted aromatic diamine include 1,2-, 1,3- or 1,4-phenylenediamine, 2,4'-or 4,4'-diphenylmethanediamine, diaminodiphenylsulfone, benzidine, thiodianiline, and bis (3). , 4-Diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, naphthylene diamine and mixtures thereof.

Aromatic diamines having an alkyl group (alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n- or isopropyl group and butyl group) include 2,4- or 2,6-tolylene diamine and crude. Tolylene diamine, diethyl tolylene diamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditril sulfone, 1,3-dimethyl-2 , 4-Diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl -2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomethicylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-tri Isopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 2,3-dimethyl-1 , 4-Diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-1,5-diaminonaphthalene, 3,3', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetraisopropylbenzidine, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3', 5 , 5'-Tetraethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-Tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-Tetrabutyl-4,4 '-Diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2', 4-diaminodiphenylmethane, 3,5-diisopropyl-3'-methyl-2', 4-diaminodiphenylmethane, 3,3'-diethyl- 2,2'-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3', 5, 5'-Tetraisopropyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5'-tetraisopropyl-4,4 '-Diaminodiphenylsulfone and mixtures thereof, etc. Can be mentioned.

Crystalline polyamide (a14)
Examples of the crystalline polyamide (a14) include a polycondensate of the crystalline polyester (a11), the diamine (z), and the dicarboxylic acid component (y). Such a crystalline polyamide (a14) can be obtained by reacting the crystalline polyester (a11) with the diamine (z) and a dicarboxylic acid component.

Crystalline polyvinyl resin (a15)
Examples of the crystalline polyvinyl resin (a15) include polymers obtained by homopolymerizing or copolymerizing an ester having a polymerizable double bond.
Esters having a polymerizable double bond include vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, and phenyl (meth). ) Acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and eicocil (meth) acrylate, etc.], Dialkyl fumarate (two alkyl groups) Is a linear, branched or alicyclic group having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms). The basis of the formula), poly (meth) allyloxyalkane compounds (dialyloxyetane, triallyloxyetane, tetraaryloxyetane, tetraaryloxypropane, tetraaryloxybutane, tetramethalyloxyetane, etc.), etc. Monomer having a polymerizable double bond with a polyalkylene glycol chain [polyethylene glycol (Mn = 300) mono (meth) acrylate, polypropylene glycol (Mn = 500) mono acrylate, methyl alcohol EO 10 mol adduct (meth) acrylate and Lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylate [poly (meth) acrylate of polyhydric alcohol: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.] and the like.

The crystalline polyvinyl resin (a15) can be composed of the following compounds (w1) to (w9) in addition to the ester having a polymerizable double bond.

Monomer (w1) Hydrocarbon with polymerizable double bond:
For example, the following (w11) aliphatic hydrocarbons having a polymerizable double bond and (w12) aromatic hydrocarbons having a polymerizable double bond can be mentioned.
(W11) An aliphatic hydrocarbon having a polymerizable double bond:
For example, the following (w111) and (w112) can be mentioned.
(W111) Chain hydrocarbon having a polymerizable double bond: an alkene having 2 to 30 carbon atoms (for example, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadien, etc.).
(W112) Cyclic hydrocarbon having a polymerizable double bond: mono or dicycloalkene having 6 to 30 carbon atoms (for example, cyclohexene, vinylcyclohexene, etylidenebicycloheptene, etc.) and mono or dicycloalkene having 5 to 30 carbon atoms. Diene [for example, (di) cyclopentadiene, etc.] and the like.

(W12) Aromatic hydrocarbons having a polymerizable double bond:
Styrene; Hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituents of styrene (eg α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, Butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, etc.); and vinylnaphthalene, etc.

(W2) Monomers having a carboxyl group and a polymerizable double bond and salts thereof:
Unsaturated monocarboxylic acid with 3 to 15 carbon atoms {for example, (meth) acrylic acid ["(meth) acrylic" means acrylic or methacrylic. ], Crotonic acid, isocrotonic acid, cinnamic acid, etc.}; unsaturated dicarboxylic acid (anhydrous) having 3 to 30 carbon atoms [for example, (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid, mesaconic acid, etc. ]; And monoalkyl (1-10 carbon) esters of unsaturated dicarboxylic acids with 3-10 carbon atoms (eg, maleic acid monomethyl ester, maleic acid monodecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester and citracon). Acid monodecyl ester, etc.) etc.

Examples of the salt constituting the salt of the monomer having a carboxyl group and a polymerizable double bond include an alkali metal salt (sodium salt, potassium salt, etc.), an alkaline earth metal salt (calcium salt, magnesium salt, etc.), and ammonium. Examples thereof include salts, amine salts and quaternary ammonium salts.
The amine salt is not particularly limited as long as it is an amine compound, but for example, a primary amine salt (ethylamine salt, butylamine salt, octylamine salt, etc.), a secondary amine (diethylamine salt, dibutylamine salt, etc.), and a tertiary amine ( Triethylamine salt, tributylamine salt, etc.) can be mentioned. Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt and tributyllaurylammonium salt.

Examples of the salt of the monomer having a carboxyl group and a polymerizable double bond include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, and acrylic. Examples thereof include lithium acrylate, cesium acrylate, ammonium acrylate, calcium acrylate and aluminum acrylate.

(W3) Monomers having a polymerizable double bond with a sulfo group and salts thereof:
Alken sulfonic acid having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, etc.); styrene sulfonic acid and its alkyl (2 to 24 carbon atoms) derivative (for example, α-methyl styrene sulfonic acid). Acids, etc .; sulfo (hydroxy) alkyl- (meth) acrylates with 5 to 18 carbon atoms [eg, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl sulfonic acid, 2- (meth) acryloyloxy. Etan sulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropane sulfonic acid, etc.]; sulfo (hydroxy) alkyl (meth) acrylamide with 5-18 carbon atoms [eg 2- (meth) acryloylamino-2,2- Dimethylethanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, etc.]; Alkyl (3-18 carbon atoms) allylsulfosuccinic acid (eg, propylallyl) Sulfonic acid, butylallyl sulfosuccinic acid, 2-ethylhexyl-allyl sulfosuccinic acid, etc.); Poly [n (polymerization degree; the same applies hereinafter) = 2 to 30] oxyalkylene (oxyethylene, oxypropylene, oxybutylene, etc. It may be used alone or in combination, and when used in combination, the addition form may be random addition or block addition.) Sulfonate of mono (meth) acrylate [eg, poly (n = 5-15) oxyethylene monomethacrylate sulfate and poly (n). = 5 to 15) Oxypropylene monomethacrylate sulfate and the like]; and salts thereof and the like.

Examples of the salt include those exemplified as a salt constituting a (w2) carboxyl group and a monomer having a polymerizable double bond.

(W4) Monomer having a phosphono group and a polymerizable double bond and a salt thereof:
(Meta) Acryloyloxyalkyl Phosphonate (1-24 carbon atoms of alkyl group) (eg 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, etc.), (meth) acryloyloxyalkyl Phosphonate (1 to 24 carbon atoms of the alkyl group) (eg 2-acryloyloxyethyl phosphonic acid, etc.).
Examples of the salt include those exemplified as the salt constituting the (w2) carboxyl group and the monomer having a polymerizable double bond.

(W5) Monomer having a hydroxyl group and a polymerizable double bond:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, allyl ether and the like.

(W6) Nitrogen-containing monomer having a polymerizable double bond:
For example, (w61) a monomer having a polymerizable double bond with an amino group, (w62) a monomer having a polymerizable double bond with an amide group, and (w63) a carbon having a polymerizable double bond with a nitrile group. Examples thereof include a monomer having a number of 3 to 10, a monomer having a (w64) nitro group and a polymerizable double bond, and a monomer having 8 to 12 carbon atoms.
(W61) Monomer having a polymerizable double bond with an amino group:
Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole , Aminothiazole, Aminoindole, Aminopyrol, Aminoimidazole, Aminomercaptothiazole and salts thereof.

(W62) Monomer having a polymerizable double bond with an amide group:
(Meta) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N'-methylene-bis (meth) acrylamide, cinnamic acid amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
(W63) Monomer having 3 to 10 carbon atoms having a polymerizable double bond with a nitrile group:
(Meta) Acrylonitrile, cyanostyrene, cyanoacrylate, etc.
(W64) Monomer having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond:
Nitrostyrene etc.

(W7) Monomer having 6 to 18 carbon atoms having a polymerizable double bond with an epoxy group:
Glycidyl (meth) acrylate, p-vinylphenylphenyloxide, etc.

(W8) Monomer having 2 to 16 carbon atoms having a polymerizable double bond with a halogen element:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromstyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(W9) Ether having a polymerizable double bond, a ketone having a polymerizable double bond, and a sulfur-containing compound having a polymerizable double bond:
For example, (w91) an ether having 3 to 16 carbon atoms having a polymerizable double bond, (w92) a ketone having 4 to 12 carbon atoms having a polymerizable double bond, and (w93) having a carbon number of carbon atoms having a polymerizable double bond. Examples thereof include 2 to 16 sulfur-containing compounds.
(W91) Ether having 3 to 16 carbon atoms having a polymerizable double bond:
Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro -1,2-Pyran, 2-Butoxy-2'-vinyloxydiethyl ether, acetoxystyrene, phenoxystyrene and the like can be mentioned.
(W92) Ketone having 4 to 12 carbon atoms having a polymerizable double bond:
Examples thereof include vinyl methyl ketone, vinyl ethyl ketone and vinyl phenyl ketone.
(W93) A sulfur-containing compound having a polymerizable double bond and having 2 to 16 carbon atoms:
Examples thereof include divinyl sulphide, p-vinyl diphenyl sulphide, vinyl ethyl sulphide, vinyl ethyl sulfone, divinyl sulfone and divinyl sulfoxide.

The crystalline resin (A) of the present invention is a chart by DSC measured by a differential scanning calorimeter (DSC), and is the first when the temperature of the toner binder is raised from 30 ° C. to 180 ° C. under the condition of 10 ° C./min. The endothermic peak of the first endothermic process is cooled to 0 ° C under the condition of S ₁ (J / g) at 10 ° C / min and then raised to 180 ° C under the condition of 10 ° C / min. When the endothermic amount of the endothermic peak in the second temperature rise process is S ₂ (J / g), the endothermic amounts S ₁ and S ₂ of the endothermic peak at the time of temperature rise satisfy the following relational expression (1). It is preferable from the viewpoints of low temperature fixing property, fluidity, heat storage property, crushability, image strength after fixing, bending resistance and document offset property of the toner.
35 ≦ (S ₂ / S ₁ ) × 100 ≦ 100 (1)

In the present invention, the temperature raising / cooling conditions for measuring the crystalline resin (A), the toner binder, and the like by DSC are as follows. (1) The temperature is raised from 30 ° C. to 180 ° C. under the condition of 10 ° C./min (first temperature raising process). (2) Next, after leaving it at 180 ° C. for 10 minutes, it is cooled to 0 ° C. under the condition of 10 ° C./min (first cooling process). (3) Next, the temperature is raised to 180 ° C. under the condition of 10 ° C./min after being left at 0 ° C. for 10 minutes (second temperature raising process).

When the crystalline resin (A) has two or more endothermic peaks, both S ₁ and S ₂ are calculated by the total endothermic amount.
The endothermic amount (area) of the endothermic peak is calculated by drawing a line perpendicular to the baseline at the valley of the peak and dividing the area, and using the area divided by the dividing line.
If the peak can be identified, DSC may be measured using a toner binder or toner as the sample instead of the crystalline resin (A).
When a toner binder or a toner is used as a sample, if the endothermic peak of the crystalline resin (A) overlaps with the endothermic peak of the crystalline resin (A), it is decomposed into each peak and the crystalline resin (A). Find the endothermic amount of the endothermic peak of. Of the raw materials further blended in the toner binder, crystalline raw materials such as wax may develop an endothermic peak.

The value of (S ₂ / S ₁ ) × 100 in the relational expression (1) is more preferably 40 to 99, still more preferably 50 to 98.

The endothermic amount (J / g) of the endothermic peak of the crystalline resin (A) in the second temperature raising process is preferably 1 to 30 J / g, more preferably 2 to 25 J / g, and further preferably 3 to 20 J / g. g. From the viewpoint of low-temperature fixability and gloss, the endothermic heat of the crystalline resin (A) is preferably 1 J / g or more, and from the viewpoint of hot melt resistance, it is preferably 30 J / g or less.

In order for the crystalline resin (A) to satisfy the relational expression (1), it is a linear or branched aliphatic diol (x1) having 2 to 12 carbon atoms as a constituent component of (A), preferably an alcohol component (x). ), The carboxylic acid component (y) contains an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and the alcohol component (x) includes a long-chain alkyl monoalcohol (preferably 18 to 42 carbon atoms) and a carboxylic acid component (preferably 18 to 42 carbon atoms). As y), it contains a compound selected from the group consisting of long-chain alkyl monocarboxylic acids (preferably 18 to 42 carbon atoms).

The weight average molecular weight of the crystalline resin (A) (hereinafter, the weight average molecular weight may be abbreviated as Mw) is preferably 8,000 to 150,000, more preferably 150,000, from the viewpoint of low temperature fixability and glossiness. Is 10,000 to 110,000, particularly preferably 12,000 to 100,000.
For Mw and number average molecular weight (also referred to as Mn in the present specification), crystalline resin (A) is dissolved in tetrahydrofuran (THF), and gel permeation chromatography (GPC) is used as a sample solution. It is measured under the following conditions.
Equipment (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μL
Detection device: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000
2890000)

The toner binder of the present invention contains a polyester resin (B) containing an alcohol component (x) and a carboxylic acid component (y) as constituent raw materials for hot offset resistance, chargeability, and thermal stability of a fixed image. Preferred from the viewpoint.

The weight ratio (B / A) of the amorphous polyester resin (B) to the crystalline resin (A) is the fluidity of the toner, heat storage stability, pulverizability, image strength after fixing, low temperature fixing property and glossiness. From the viewpoint, it is preferably 50/50 to 95/5, more preferably 60/40 to 92/8, and even more preferably 70/30 to 90/10. A mixture containing the amorphous polyester resin (B) and the crystalline resin (A) in the above proportions is preferable as the toner binder of the present invention. That is, the weight ratio (B / A) of the amorphous polyester resin (B) and the crystalline resin (A) in the toner binder of the present invention is preferably in the above range.

In the present invention, when the glass transition point (Tg ₁ +30) (° C.) of the amorphous polyester resin (B) is the same as or higher than the temperature Tp (° C.) indicating the heat absorption peak top of the crystalline resin (A), ( At the temperature of Tg ₁ +30), when (Tg ₁ +30) is lower than Tp, at the temperature of Tp, preferably the whole or a part of the toner binder is turbid, and more preferably a part of the toner binder is turbid.
A mixture of the amorphous polyester resin (B) and the crystalline resin (A) is mixed at a temperature (° C.) of (Tg ₁ +30) from a temperature Tp (° C.) indicating the top of the heat absorption peak of the crystalline resin (A). It is preferable that the whole or part of the mixture is turbid when visually observed at the same or higher temperature at (Tg ₁ +30) and at the temperature of Tp when (Tg ₁ +30) is lower than Tp. If there is turbidity, it means that the crystalline resin (A) is not completely compatible with the amorphous polyester resin (B), and the crystalline resin (A) is likely to recrystallize when cooled. preferable.
When the crystalline resin (A) has two or more endothermic peaks, the temperature showing the highest endothermic peak top among them is defined as Tp in this case.

The method of mixing the amorphous polyester resin (B) and the crystalline resin (A) is not particularly specified, and for example, a method of mixing the amorphous polyester resin (B) and the crystalline resin (A) with a melt kneader. , A method of dissolving and mixing with a solvent or the like and then removing the solvent, a method of mixing the crystalline resin (A) at the time of producing the amorphous polyester resin (B), and the like. The mixing temperature is preferably 100 to 200 ° C., more preferably 110 to 190 ° C. from the viewpoint of resin viscosity.
The toner binder of the present invention can be obtained, for example, by mixing the crystalline resin (A) and the amorphous polyester resin (B) as described above.

In the following, the "segment (a2) that is incompatible with the amorphous polyester resin (B)" is referred to as "end sealant (a2) that is incompatible with the amorphous polyester resin (B)", and is referred to as ". “Segment (a2)” is referred to as “terminal sealant (a2)”.
The crystalline resin (A) is a resin in which at least two or more types of segments are chemically bonded, and is a crystalline segment (a1) compatible with the amorphous polyester resin (B) and an amorphous polyester. A resin in which a segment (a2) that is incompatible with the resin (B) is chemically bonded is preferable. In the present specification, the crystalline segment (a1) compatible with the amorphous polyester resin (B) is also simply referred to as a segment (a1) or a crystalline segment (a1). The segment (a2) that is incompatible with the amorphous polyester resin (B) is also simply referred to as a segment (a2).
In the present invention, the segment (a1) and the segment (a2) are compounds having terminal groups that react with each other.
In the present invention, incompatible with the amorphous polyester resin (B) means that when the amorphous polyester resin (B) and each segment are mixed and the mixture is visually observed at room temperature, the whole mixture or It means that there is turbidity in a part. As a method of mixing and a method of determination, the amorphous polyester resin (B) and each segment are melted and mixed while being heated in a solvent, and then 100 mg of the mixture obtained by removing the solvent is put on a slide glass (slide glass). It was heated at 130 ° C. for 10 minutes on (76 mm × 26 mm) to melt it, and then air-cooled to room temperature, and the turbidity of the mixture at that time was visually observed.

The crystalline segment (a1) includes the crystalline polyester (a11), the crystalline polyurethane (a12), the crystalline polyurea (a13), the crystalline polyamide (a14), and the crystalline polyvinyl (a15) described above. And so on.

The segment (a2) that is incompatible with the resin (B) is not particularly limited as long as it is a compound that is incompatible with the amorphous polyester resin (B). Examples of the compound that is incompatible with the amorphous polyester resin (B) include a long-chain alkyl monoalcohol (preferably 18 to 42 carbon atoms), a long chain alkyl monocarboxylic acid (preferably 18 to 42 carbon atoms), and butadiene. Examples thereof include an alcohol-modified form and an alcohol-modified form of dimethylsiloxane, preferably a long-chain alkyl monoalcohol having 18 to 42 carbon atoms, a long-chain alkyl monocarboxylic acid having 18 to 42 carbon atoms, and the like. As the segment (a2), a structure composed of such a compound is preferable. As the long-chain alkyl monoalcohol having 18 to 42 carbon atoms, for example, behenyl alcohol, stearyl alcohol and the like are preferable.

Assuming that the solubility parameter of the amorphous polyester resin (B) is SP _B , the solubility parameter of the segment (a1) is SP _a1 , and the solubility parameter of the segment (a2) is SP _a2 , the segment (a1) and the segment (a2) ) Satisfyes both the following relational expressions (2) and (3).

｜ SP _a1 -SP _B ｜ ≦ 2.0 (cal / cm ³ ) ^1/2 (2)
｜ SP _a2 -SP _B ｜ ≧ 2.0 (cal / cm ³ ) ^1/2 (3)
In the above formula, SP _a1 indicates the SP value of the segment (a1), SP _a2 indicates the SP value of the segment (a2), and SP _B indicates the SP value of the amorphous polyester resin (B).

Here, when the crystalline resin (A) is a resin in which the segment (a1) and the segment (a2) are chemically bonded by condensation, the SP value is calculated as follows.
In the case of condensation forming an ester bond, it is considered that the bonded portion of the segment (a1) and the segment (a2) is formed by dehydration condensation, and the SP values of the segment (a1) and the segment (a2) are calculated respectively. ..
In the case of condensation forming an amide bond, it is considered that the bonded portion of the segment (a1) and the segment (a2) is formed by dehydration condensation, and the SP values of the segment (a1) and the segment (a2) are calculated respectively. ..

The value on the left side of the relational expression (2) is preferably 2.0 or less, more preferably 0.1 to 1.9, from the viewpoint of compatibility between the amorphous polyester resin (B) and the segment (a1). be.
Similarly, the value on the left side of the relational expression (4) is preferably 2.0 or more, more preferably 2.1 or more, from the viewpoint of compatibility between the amorphous polyester resin (B) and the segment (a2). be. The upper limit of the left side of the relational expression (3) is preferably 4.0 or less, more preferably 3.5 or less.
By satisfying both the relational expressions (2) and (3), depopulation during heating and recrystallization during cooling are likely to occur due to the crystalline resin (A), and low temperature fixability, glossiness, and toner fluidity are likely to occur. , Heat-resistant storage stability, image strength after fixing, and bending resistance are improved.

The SP values (SP _a1, SP _a2 ) [unit: (cal / cm ³ ) ^1/2 ] of the crystalline segment (a1) and the segment (a2) in the present invention are described by the method by Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)].

In the preferable crystalline resin (A) of the present invention, it is preferable that at least the segment (a1) and the segment (a2) are chemically bonded in the same molecule. Further, the crystalline resin (A) preferably has at least one group selected from the group consisting of an ester group, a urethane group, a urea group, an amide group, an epoxy group, and a vinyl group.
Further, in addition to the combination of one type of segment (a1) and one type of segment (a2), three or more types of segments may be included, and the segment (a1) and the segment (a2) may be directly chemically bonded. Then, the segment (a1) and the segment (a3) other than the segment (a2) may be combined.
Examples of this segment (a3) include an amorphous segment that is compatible with the amorphous polyester resin (B).

Therefore, when three or more types of segments are included, for example, a combination of one type of segment (a1), one type of segment (a2) and one type of segment (a3), two types of segments (a1) and one. Examples include a combination of seed segments (a2), a combination of one segment (a1) and two segments (a2), and the like. Here, as an example of two or more types of segments, there is a case where the molecular weight and other physical properties are different even if the type of chemical structure (for example, polyester) is the same.

The chemical bond is preferably at least one group selected from the group consisting of an ester group, a urethane group, a urea group, an amide group, and an epoxy group from the viewpoint of low temperature fixability, and from the same viewpoint, the ester group and urethane. Groups are even more preferred.
In the present invention, the segment (a1) and the segment (a2) in the crystalline resin (A) are one or more functional groups selected from the group consisting of an ester group, a urethane group, a urea group, an amide group and an epoxy group. It is preferably bonded with a group. As described above, the crystalline resin (a1) and the segment (a2) are bonded by one or more functional groups selected from the group consisting of an ester group, a urethane group, a urea group, an amide group and an epoxy group (a crystalline resin). A) is preferable as the crystalline resin (A) in the present invention.

The amorphous polyester resin (B) used for the toner and the toner binder of the present invention is a polyester resin obtained by reacting an alcohol component (X) and a carboxylic acid component (Y) as raw materials, and is a crystalline resin (a crystalline resin). The composition of the resin is not particularly limited as long as it excludes A). The alcohol component (X) is preferably a polyol component such as a diol.
The amorphous polyester resin (B) may be modified, and the modified resin has at least one group selected from the group consisting of a urethane group, a urea group, an amide group, an epoxy group and a vinyl group. It may be a resin.
Examples of the polyester resin (B) include an amorphous polyester resin (B1), an amorphous styrene (co) polymer polyester-modified resin (B2), and an amorphous epoxy resin polyester-modified resin (B3). Examples thereof include a polyester-modified resin (B4) of an amorphous urethane resin and a polyester-modified resin (B5) of an amorphous urea resin. Of these, the polyester resin (B) is preferably an amorphous polyester resin (B1).
The term "amorphous" in the present invention refers to a resin having no maximum endothermic curve in the DSC curve and no endothermic peak in the first heating process of the DSC measurement described above.

The amorphous polyester resin (B1) is a polyester resin obtained by reacting an alcohol component (X) with a carboxylic acid component (Y) as raw materials.
As the polyol component constituting the amorphous polyester resin (B1), the same diol components (x1) to (x3) used in the crystalline polyester (a11) can be used. Further, if necessary, a trivalent or higher-valent polyol (x4) and a monool (x5) can be used together with the diol components (x1) to (x3). As the trivalent or higher-valent polyol, the same one as the trivalent or higher-valent polyol used in the crystalline polyester (a11) can be used.
Examples of the monool (x5) include alkanols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.).

Among them, as the alcohol component (X), from the viewpoint of low temperature fixability and hot offset resistance, alkylene glycols having 2 to 12 carbon atoms and polyoxyalkylene ethers of bisphenol compounds (number of AO units 2 to 30) [of bisphenol A]. AO adduct (additional number of moles 2 to 30)], polyhydric aliphatic alcohols with valences of 3 to 8 or more, and polyoxyalkylene ethers of novolak resin (number of AO units 2 to 30) [novolak resin AO adduct (additional number of moles 2 to 30)] is preferable.

More preferred are alkylene glycols having 2 to 10 carbon atoms, polyoxyalkylene ethers of bisphenol compounds (number of AO units 2 to 5), and polyoxyalkylene ethers of novolak resins (number of AO units 2 to 30). Particularly preferred are alkylene glycols having 2 to 6 carbon atoms and polyoxyalkylene ethers of bisphenol A (number of AO units 2 to 5), and most preferably ethylene glycols, propylene glycols and polyoxyalkylene ethers of bisphenol A (number of AO units 2 to 5). The number of AO units is 2-3).
In order to obtain an amorphous resin, the content of the linear diol is preferably 70 mol% or less, more preferably 60 mol% or less of the diol components (x1) to (x3) used. Further, in the alcohol component (X) constituting the amorphous polyester resin (B1), the diol component (x1) is preferably 90 to 100 mol%.

As the carboxylic acid component (Y) constituting the amorphous polyester resin (B1), the same dicarboxylic acid component (y1) used in the crystalline polyester (a11) can be used. Further, if necessary, a trivalent or higher polycarboxylic acid (y2) and a monocarboxylic acid (y3) can be used together with the dicarboxylic acid component (y1). As the trivalent or higher valent polycarboxylic acid, the same polycarboxylic acid as the trivalent or higher valent polycarboxylic acid used in the crystalline polyester (a11) can be used.
Among the monocarboxylic acids (y3), the aliphatic (including alicyclic) monocarboxylic acid is an alkane monocarboxylic acid having 1 to 30 carbon atoms (formic acid, acetic acid, propionic acid, butanoic acid, isobutanoic acid, capric acid). , Capric acid, lauric acid, myristyl acid, palmitic acid, stearic acid, behenic acid, cellotic acid, monitor acid, melicic acid, etc.), alkenemonocarboxylic acid with 3 to 24 carbon atoms (acrylic acid, methacrylic acid, oleic acid, etc.) Linol acid, etc.) and the like. Among (x1), the aromatic monocarboxylic acid has 7 to 36 carbon atoms (benzoic acid, methylbenzoic acid, pt-butylbenzoic acid, phenylpropionic acid, naphthoic acid, etc.) and the like. Can be mentioned.

Among these carboxylic acid components, benzoic acid, arcandicarboxylic acid having 2 to 50 carbon atoms, arcendicarboxylic acid having 4 to 50 carbon atoms, and 8 to 20 carbon atoms from the viewpoint of achieving both low temperature fixing property and hot offset resistance. Aromatic dicarboxylic acid and aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimertic acid, pyromellitic acid, etc.) are preferable.
More preferably, it is benzoic acid, adipic acid, alkenyl succinic acid having 16 to 50 carbon atoms, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid, and a combination of two or more thereof. , Particularly preferred are adipic acid, terephthalic acid, trimellitic acid, and a combination of two or more of these.
Anhydrides and lower alkyl esters of these carboxylic acids are also preferred.

The glass transition point (Tg) of the amorphous polyester resin (B) is determined from the viewpoints of low temperature fixability, glossiness and toner fluidity, heat storage stability, image strength after fixing, bending resistance, and document offset property. It is preferably 40 to 75 ° C, more preferably 45 to 72 ° C, and particularly preferably 50 to 70 ° C.
In addition, Tg is measured by the method (DSC method) specified in ASTM D3418-82 using DSC.

The Mw of the amorphous polyester resin (B1) has 2 from the viewpoints of low temperature fixability, glossiness and toner fluidity, heat storage stability, crushability, image strength after fixing, bending resistance, and document offset property. It is preferably 3,000 to 200,000, more preferably 2,500 to 150,000, and particularly preferably 3,000 to 120,000.
The Mw and Mn of the amorphous polyester resin (B) are obtained by GPC in the same manner as the above-mentioned crystalline resin (A).

The acid value of the amorphous polyester resin (B) is low temperature fixability, glossiness and toner fluidity, heat storage stability, charge stability, crushability, image strength after fixing, bending resistance, and document offset property. From the viewpoint, it is preferably 30 mgKOH / g or less, more preferably 20 mgKOH / g or less, and further preferably 15 mgKOH / g or less.
In the present invention, the acid value can be measured by the method specified in JIS K0070.

The method for reducing the acid value of the amorphous polyester resin (B) is not particularly limited, but for example, the molecular weight is increased, the amount of trimellitic anhydride charged for half-esterification is reduced, and the end is capped with a monoalcohol or the like. The cross-linking reaction is carried out with a trifunctional or higher functional acid or alcohol, and the ratio of the acid and alcohol charged in urethane or the like is adjusted so that the amount of alcohol is slightly excessive to make the terminal functional group alcohol.

The hydroxyl value of the amorphous polyester resin (B) has low temperature fixability, glossiness and toner fluidity, heat storage stability, charge stability, crushability, image strength after fixing, bending resistance, and document offset property. From the viewpoint, 60 mgKOH / g or less is preferable, and 50 mgKOH / g or less is more preferable.
In the present invention, the hydroxyl value can be measured by the method specified in JIS K0070.

The method for reducing the hydroxyl value of the amorphous polyester resin (B) is not particularly limited, but for example, the cross-linking reaction is carried out with a trifunctional or higher functional acid or alcohol that increases the molecular weight and caps the ends with a monocarboxylic acid or the like. , Urethane and other charged acids and alcohol ratios are adjusted so that the amount of acid is slightly excessive to make the terminal functional group acid.

The content of the molecule of the amorphous polyester resin (B) having a molecular weight of 1,000 or less includes the fluidity of the toner, heat storage stability, charge stability, pulverizability, image strength after fixing, bending resistance, and document offset property. From the viewpoint of the above, when expressed by the peak area when the molecular weight of the amorphous polyester resin (B) is measured by gel permeation chromatography, it is preferably 10% or less, more preferably 8% or less of the total peak area. Yes, more preferably 6% or less. It is particularly preferably 4% or less, and most preferably 2% or less. When the content of the molecule having a molecular weight of 1,000 or less contained in the amorphous polyester resin (B) is within the above range, the fluidity of the toner, the heat storage stability, the charge stability, the pulverizability, the image strength after fixing, and the like. Good bending resistance and document offset.

The content of the molecule having a molecular weight of 1,000 or less of the amorphous polyester resin (B) in the present invention is obtained by processing the molecular weight measurement result of the amorphous polyester resin (B) by the above-mentioned GPC as follows. Ask.
(1) Obtain the holding time at which the molecular weight becomes 1,000 from the calibration curve centered on the molecular weight and the holding time.
(2) Obtain the total peak area (Σ1).
(3) The peak area (peak area having a molecular weight of 1,000 or less) (Σ2) after the holding time obtained in (1) is obtained.
(4) The content of a molecule having a molecular weight of 1,000 or less is obtained from the following formula.
Content of molecules with a molecular weight of 1,000 or less (%) = (Σ2) × 100 / (Σ1)

The method for reducing the content of molecules having a molecular weight of 1,000 or less in the amorphous polyester resin (B) is not particularly limited, but for example, the molecular weight of the amorphous polyester resin (B) is increased, and the terminal is a monocarboxylic acid or the like. The cross-linking reaction may be carried out with a trifunctional or higher functional acid or the like capped with.

The softening point (Tm) measured by the flow tester of the amorphous polyester resin (B) is preferably 80 to 170 ° C, more preferably 85 to 165 ° C, and particularly preferably 90 to 160 ° C.

The softening point (Tm) is measured by the following method.
Using a high-grade flow tester {for example, CFT-500D manufactured by Shimadzu Corporation}, a load of 1.96 MPa is applied by a plunger while heating 1 g of the measurement sample at a temperature rise rate of 6 ° C./min. , Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of "plunger drop amount (flow value)" and "temperature", and set the temperature corresponding to 1/2 of the maximum value of the plunger drop amount. Read from the graph, and let this value (the temperature when half of the measurement sample flows out) be the softening point [Tm].

Two or more kinds of amorphous polyester resins (B) having different Tms may be used in combination, and a combination of one having a Tm of 80 to 110 ° C and one having a Tm of 110 to 170 ° C is preferable.

As the amorphous polyester resin (B) in the present invention, a polyester-modified resin (B2) of an amorphous styrene (co) polymer can also be used.
The polyester-modified resin (B2) of this amorphous styrene (co) polymer is a polymer of a styrene monomer alone or a polymer of a styrene monomer and a (meth) acrylic monomer reacted with polyester.
Examples of the styrene monomer include styrene and alkylstyrene having an alkyl group having 1 to 3 carbon atoms (for example, α-methylstyrene and p-methylstyrene). Styrene is preferable.

Examples of the (meth) acrylic monomer that can be used in combination include alkyls such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. Alkyl esters with 1 to 18 carbon atoms in the group; hydroxyl group-containing (meth) acrylates with 1 to 18 carbon atoms in alkyl groups such as hydroxylethyl (meth) acrylates; dimethylaminoethyl (meth) acrylates, diethylaminoethyl (meth) Amino group-containing (meth) acrylates with 1 to 18 carbon atoms of alkyl groups such as acrylates; nitrile group-containing (meth) groups in which the methyl groups of acrylonitrile, methacrylonitrile, and methacrylonitrile are replaced with alkyl groups having 2 to 18 carbon atoms. ) Acrylate compounds, (meth) acrylic acid and the like can be mentioned.
Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid; and a mixture of two or more thereof are preferable.

If necessary, another vinyl ester monomer or an aliphatic hydrocarbon vinyl monomer may be used in combination with the polyester-modified resin (B2) of the amorphous styrene (co) polymer.
Examples of the vinyl ester monomer include aliphatic vinyl esters (4 to 15 carbon atoms such as vinyl acetate, vinyl propionate, isopropenyl acetate, etc.) and unsaturated carboxylic acid polyvalent (2 to 3 valent) alcohol esters (8 to 200 carbon atoms). For example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethyl propantri (meth) acrylate, 1,6-hexanediol diacrylate and polyethylene glycol di (meth). ) Acrylate, etc.), aromatic vinyl ester (9 to 15 carbon atoms, for example, methyl-4-vinylbenzoate, etc.) and the like.
Examples of the aliphatic hydrocarbon vinyl monomer include olefins (2 to 10 carbon atoms such as ethylene, propylene, butene and octene) and dienes (4 to 10 carbon atoms such as butadiene, isoprene and 1,6-hexadiene). Be done.

The Mw of the polyester-modified resin (B2) of the amorphous styrene (co) polymer used in the present invention is Mw 100,000 to 300,000, preferably 130,000 to 300,000 from the viewpoint of the fixing temperature range. It is 280,000, more preferably 150,000 to 250,000.

Further, the ratio Mw / Mn of the Mw of the polyester-modified resin (B2) of the amorphous styrene (co) polymer to the number average molecular weight (Mn) is preferably, for example, 10 to 70 from the viewpoint of the fixing temperature range. It is more preferably 15 to 65, still more preferably 20 to 60.

It is preferable to use two or more kinds of the amorphous styrene (co) polymer polyester-modified resin (B2) having different molecular weights from the viewpoint of the fixing temperature range.

As the amorphous polyester resin (B) in the present invention, a polyester-modified resin (B3) of an amorphous epoxy resin can also be used.
Examples of the polyester-modified resin (B3) of the amorphous epoxy resin include a ring-opening polymer of polyepoxy, polyepoxy and an active hydrogen-containing compound {water, a polyol [diol and a trivalent or higher polyol], a dicarboxylic acid, and a trivalent or higher. Examples thereof include those obtained by reacting a heavy adduct with a polycarboxylic acid, a polyamine, etc. with polyester.

Further, as the amorphous polyester resin (B) in the present invention, a polyester modified resin (B4) of an amorphous urethane resin can also be used.
Examples of the polyester-modified resin (B4) of the amorphous urethane resin include those obtained by reacting the above-mentioned diisocyanate (v2), monoisocyanate (v1), trifunctional or higher polyisocyanate (v3) with polyester, and the like. ..

Examples of the monoisocyanate (v1) include phenyl isocyanate, tolylene isocyanate, xylylene isocyanate, α, α, α', α'-tetramethylxylylene isocyanate, naphthylene isocyanate, ethyl isocyanate, propyl isocyanate, hexyl isocyanate and octyl isocyanate. , Decyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, cyclobutyl isocyanate, cyclohexyl isocyanate, cyclooctyl isocyanate, cyclodecyl isocyanate, cyclododecyl isocyanate, cyclotetradecyl isocyanate Nate, isophorone isocyanate, dicyclohexylmethane-4-isocyanate, cyclohexylene isocyanate, methylcyclohexylene isocyanate, norbornan isocyanate and bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and the like can be mentioned.

The trifunctional or higher polyisocyanate (v3) is not particularly limited as long as it is a compound having three or more isocyanate groups, and examples thereof include triisocyanate, tetraisocyanate, isocyanurate, and compounds containing a chemical structure of biuret. Be done.

The toner binder of the present invention may be made of a crystalline resin (A) and an amorphous polyester resin (B), and may contain other components as necessary as long as the effects of the present invention are not impaired. good. A toner binder made of a crystalline resin (A) and an amorphous polyester resin (B) is preferable.

The total content of the crystalline resin (A) and the amorphous polyester resin (B) in the present invention is preferably 90 to 100% by weight based on the weight of the toner binder from the viewpoint of low temperature fixability. More preferably, it is 95 to 100% by weight.

The crystalline resin (A) in the present invention can be produced in the same manner as a known resin production method.
For example, the crystalline polyester (a11) in the present invention can be produced in the same manner as the polyester production method known for polyester resin. For example, the reaction temperature of the polyol component (x) and the polycarboxylic acid component (y) in an inert gas (nitrogen gas or the like) atmosphere is preferably 150 to 280 ° C, more preferably 170 to 260 ° C, and particularly preferably. Can be carried out by reacting at 180 to 240 ° C., most preferably 200 to 230 ° C. The reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction.
At this time, an esterification catalyst can be used if necessary. Examples of esterification catalysts include tin-containing catalysts (eg dibutyltin oxide), antimony trioxide, titanium-containing catalysts [eg titanium alkoxide (tetrabutoxytitanate), potassium titanate oxalate, titanium terephthalate, titanium terephthalate alkoxide, and the like. The catalysts described in Kai 2006-243715 [Titanium dihydroxybis (triethanol aminate), titanium monohydroxytris (triethanol aminate), and their intramolecular polycondensates, etc.], and JP-A-2007-11307. Examples thereof include catalysts described in the publication (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.)], zirconium-containing catalysts (for example, zirconyl acetate), zinc acetate, and the like. Of these, a titanium-containing catalyst is preferable. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.
The reaction ratio between the polyol component (x) and the polycarboxylic acid component (y) is preferably 2/1 to 1/2, more preferably 1. It is 5/1 to 1 / 1.3, particularly preferably 1.4 / 1 to 1 / 1.2.

A toner containing the toner binder and the colorant of the present invention is also one of the present inventions.
The toner of the present invention is preferably a composition containing a toner binder and a colorant composed of an amorphous polyester resin (B) and a crystalline resin (A).

As the colorant, all dyes, pigments and the like used as colorants for toner can be used.
Specifically, Carbon Black, Iron Black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgasin Red, Paranitroaniline Red, Truisin Red, Carmine FB, Pigment Orange R, Lake Red. 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phtalocyanin Blue, Pigment Blue, Brilliant Green, Phtalussinin Green, Oil Yellow GG, Kayaset YG, Orazole Brown B, Oil Pink OP, etc. Alternatively, two or more types can be mixed and used.
Further, if necessary, a magnetic powder (powder of a ferromagnetic metal such as iron, cobalt, nickel or a compound such as magnetite, hematite, ferrite) can be contained also having a function as a colorant.

The content of the toner binder in the present invention is preferably 75 to 95 parts by weight, more preferably 80 to 90 parts by weight, when the toner is 100 parts by weight.
The content of the colorant in the present invention is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight, when the toner is 100 parts by weight.
When magnetic powder is used, it is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight, based on 100 parts by weight of the toner.

In addition to the crystalline resin (A), the amorphous polyester resin (B), and the colorant, the toner of the present invention is added with one or more selected from a mold release agent, a charge control agent, a fluidizing agent, and the like, if necessary. Contains the agent.
The release agent preferably has a softening point [Tm] of 50 to 170 ° C. by a flow tester, and is preferably a polyolefin wax, a natural wax, an aliphatic alcohol having 30 to 50 carbon atoms, a fatty acid having 30 to 50 carbon atoms, and these. Examples include mixtures.

The polyolefin wax is obtained by (co) polymerizing a (co) polymer of an olefin (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and a mixture thereof). And heat-reduced molded polyolefins], oxides of oxygen and / or ozone of (co) polymers of olefins, maleic acid modified products of (co) polymers of olefins [eg, maleic acid and its esterifieds (maleic anhydride). , Monomethyl maleate, monobutyl maleate, dimethyl maleate, etc.) modified products], olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [((meth) acrylic acid, itaconic acid, maleic anhydride, etc.)] Meta) Polymers with alkyl acrylates (alkyls having 1 to 18 carbon atoms) and alkyl maleates (alkyls having 1 to 18 carbon atoms)] and the like, and sazole waxes and the like can be mentioned.

Examples of the natural wax include carnauba wax, montan wax, paraffin wax and rice wax. Examples of the aliphatic alcohol having 30 to 50 carbon atoms include toriacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid.

Charge control agents include niglocin dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal azo dyes, copper phthalocyanine dyes, etc. Examples thereof include salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluoropolymers, halogen-substituted aromatic ring-containing polymers and the like.

Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder and the like.

The method for producing the toner of the present invention is not particularly limited.
The toner of the present invention may be obtained by any of known kneading and pulverizing methods, emulsification phase inversion methods, polymerization methods and the like.
For example, when the toner is obtained by the kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry-blended, melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. By further classification, fine particles having a volume average particle diameter (D50) of preferably 5 to 20 μm can be obtained, and then a fluidizing agent can be mixed to produce the particles.
The volume average particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].
When toner is obtained by the emulsification phase inversion method, the components constituting the toner other than the fluidizing agent may be dissolved or dispersed in an organic solvent, then emulsified by adding water or the like, and then separated and classified for production. can. The volume average particle size of the toner is preferably 3 to 15 μm.

The toner of the present invention is electrically latent by being mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.), if necessary. Used as an image developer. The weight ratio of the toner to the carrier particles is preferably 1/99 to 100/0 for the toner / carrier particles. Further, instead of the carrier particles, it can be rubbed with a member such as a charged blade to form an electrical latent image.

The toner of the present invention is fixed to a support (paper, polyester film, etc.) by a copying machine, a printer, or the like to be used as a recording material. As a method for fixing to the support, a known heat roll fixing method, flash fixing method, or the like can be applied.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Production Example 1
[Synthesis of crystalline segment (a1-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 627 parts by weight (99.6 mol%) of 1,10-decanediol (x1a-1, Mw; 174), 1,9-nonanediol ( x1b-1, Mw; 160) 2 parts by weight (0.4 mol%), 491 parts by weight of adipic acid and 0.5 part by weight of tetrabutoxytitanate as a condensation catalyst are added, and water produced under a nitrogen stream at 170 ° C. Was reacted for 8 hours while distilling off. Then, while gradually raising the temperature to 220 ° C., the reaction was carried out under a nitrogen stream for 4 hours while distilling off the generated water, and further reacted under a reduced pressure of 0.5 to 2.5 kPa, and the acid value was 2.0 mgKOH. It was taken out when it became / g or less. The removed resin was cooled to room temperature and then pulverized into particles to obtain a crystalline polyester (a1-1). The SP _a1 of the crystalline polyester (a1-1) was 9.9 (cal / cm ³ ) ^1/2 , the acid value was 1.6 mgKOH / g, and the hydroxyl value was 26 mgKOH / g.

Manufacturing example 2
[Synthesis of crystalline segment (a1-2)]
In Production Example 1, the raw materials used are 435 parts by weight (98.1 mol%) of 1,6-hexanediol (x1a-2, Mw; 118) and 1,7-heptanediol (x1b-2, Mw; 132). The reaction was carried out in the same manner as in Production Example 1 except that 10 parts by weight (1.9 mol%) and 684 parts by weight of azelaic acid [Emerox 1144, manufactured by Emeryoleo Chemicals Japan Co., Ltd.] were carried out, and crystalline polyester (a1-2) was used. Got The SP _a2 of the crystalline polyester (a1-2) was 10.0 (cal / cm ³ ) ^1/2 , the acid value was 1.8 mgKOH / g, and the hydroxyl value was 18 mgKOH / g.

Production example 3
[Synthesis of crystalline segment (a1-3)]
In Production Example 1, the raw materials used were 1,6-hexanediol (x1a-3, Mw; 118), 415 parts by weight (99.4 mol%), and 1,7-heptanediol (x1b-3, Mw; 132). ) The reaction was carried out in the same manner as in Production Example 1 except that the content was 3 parts by weight (0.6 mol%) and 707 parts by weight of sebacic acid to obtain crystalline polyester (a1-3). The SP _a3 of the crystalline polyester (a1-3) was 9.9 (cal / cm ³ ) ^1/2 , the acid value was 1.6 mgKOH / g, and the hydroxyl value was 8 mgKOH / g.

Production example 4
[Synthesis of crystalline segment (a1-4)]
In Production Example 1, the raw materials used are 1,4-butanediol (x1a-4, Mw; 90) 332 parts by weight (99.1 mol%), 2-methyl-1,4-butanediol (x1b-4, Mw; 104) The reaction was carried out in the same manner as in Production Example 1 except that the content was 3 parts by weight (0.9 mol%) and 787 parts by weight of dodecanedioic acid to obtain crystalline polyester (a1-4). The SP _a4 of the crystalline polyester (a1-4) was 10.0 (cal / cm ³ ) ^1/2 , the acid value was 1.4 mgKOH / g, and the hydroxyl value was 34 mgKOH / g.

Production Example 5
[Synthesis of crystalline segment (a1-5)]
In Production Example 1, 508 parts by weight (99.4 mol%) of 1,9-nonanediol (x1a-5, Mw; 160), 2-methyl-1,8-octanediol (x1b-5,) were used as raw materials. Mw; 160) The reaction was carried out in the same manner as in Production Example 1 except that 3 parts by weight (0.6 mol%) and 594 parts by weight of sebacic acid were used to obtain crystalline polyester (a1-5). The SP _a5 of the crystalline polyester (a1-5) was 9.8 (cal / cm ³ ) ^1/2 , the acid value was 1.7 mgKOH / g, and the hydroxyl value was 29 mgKOH / g.

Production Example 6
[Synthesis of crystalline segment (a1-6)]
In Production Example 1, the raw materials used were 1,12-dodecanediol (x1a-6, Mw; 202) 647 parts by weight (97.0 mol%), 2-methyl-1,11-undecanediol (x1b-6, Mw; 202) 20 parts by weight (3.0 mol%) and 440 parts by weight of adipic acid were reacted in the same manner as in Production Example 1 to obtain crystalline polyester (a1-6). The SP _a6 of the crystalline polyester (a1-6) was 9.8 (cal / cm ³ ) ^1/2 , the acid value was 1.8 mgKOH / g, and the hydroxyl value was 32 mgKOH / g.

Production example 7
[Synthesis of crystalline segment (a1-7)]
In Production Example 1, the raw materials used were 1,9-nonanediol (x1a-7, Mw; 160) 667 parts by weight (99.1 mol%), 1,10-decanediol (x1b-7, Mw; 174). The reaction was carried out in the same manner as in Production Example 1 except that 7 parts by weight (0.9 mol%) and 469 parts by weight of succinic acid were used to obtain crystalline polyester (a1-7). The SP _a7 of the crystalline polyester (a1-7) was 10.2 (cal / cm ³ ) ^1/2 , the acid value was 1.4 mgKOH / g, and the hydroxyl value was 26 mgKOH / g.
Production Example 8
[Synthesis of crystalline segment (a1-8)]
In Production Example 1, the raw materials used are 1,6-hexanediol (x1a-8, Mw; 118) 423 parts by weight (99.8 mol%), 1,7-heptanediol (x1b- 8 , Mw; 132). The reaction was carried out in the same manner as in Production Example 1 except that 1 part by weight (0.2 mol%) and 701 parts by weight of sebacic acid were used to obtain crystalline polyester ( a1-8 ). The SP _a8 of the crystalline polyester (a1-8) was 10.0 (cal / cm ³ ) ^1/2 , the acid value was 1.6 mgKOH / g, and the hydroxyl value was 13 mgKOH / g.

Production Example 9
[Synthesis of crystalline segment (a1-9)]
In Production Example 1, the raw materials used were 1,12-dodecanediol (x1a-9, Mw; 202) 492 parts by weight (90.0 mol%), 1,11-undecanediol (x1b-9, Mw; 188). Production Example 1 except for 5 parts by weight (0.9 mol%), 86 parts by weight (9.1 mol%) of bisphenol A propylene oxide 2 mol addition (x2, Mw; 348), and 507 parts by weight of sebacic acid. The reaction was carried out in the same manner as in the above to obtain crystalline polyester (a1-9). The SP _a9 of the crystalline polyester (a1-9) was 9.7 (cal / cm ³ ) ^1/2 , the acid value was 1.5 mgKOH / g, and the hydroxyl value was 22 mgKOH / g.

Production Example 10
[Segment (a2-1)]
Stearyl alcohol was used as (a2-1). SP _a2 is 9.5 (cal / cm ³ ) ^1/2 .

Production Example 11
[Segment (a2-2)]
Behenyl alcohol was used as (a2-2). SP _a2 is 9.3 (cal / cm ³ ) ^1/2 .

Comparative manufacturing example 1
[Synthesis of crystalline segment (a'1-1)]
In Production Example 1, the reaction was the same as in Production Example 1 except that the raw materials used were 628 parts by weight (100 mol%) of 1,10-decanediol (x1a'-1, Mw; 174) and 492 parts by weight of adipic acid. Was carried out to obtain a crystalline polyester (a'1-1). The SP _a'1-1 of the crystalline polyester (a'1-1) was 9.9 (cal / cm ³ ) ^1/2 , the acid value was 1.4 mgKOH / g, and the hydroxyl value was 25 mgKOH / g.

Comparative manufacturing example 2
[Synthesis of crystalline segment (a'1-2)]
In Production Example 1, the raw materials used are 1,6-hexanediol (x1a'-2, Mw; 118) 417 parts by weight (99.1 mol%), 2-methyl-1,8-octanediol (x1b'-. 2, Mw; 160) The reaction was carried out in the same manner as in Production Example 1 except that 11 parts by weight (0.9 mol%) and 695 parts by weight of sebacic acid were used to obtain crystalline polyester (a'1-2). The SP _a'1-2 of the crystalline polyester (a'1-2) was 9.9 (cal / cm ³ ) ^1/2 , the acid value was 1.8 mgKOH / g, and the hydroxyl value was 18 mgKOH / g.

In the following production examples 12 to 22, the crystalline resin (A) was produced. In Production Examples 23 and 24, the amorphous polyester resin (B) was produced. In Comparative Production Examples 3 to 5, crystalline resin (A') for comparison was produced.
The temperature (Tp) indicating the endothermic peak top of the crystalline resin (A) was measured by the following method using a differential scanning calorimeter (DSC).
Equipment: Q Series Version 2.8.0.394 (manufactured by TA Instruments)
The patterns of temperature rise, cooling, and temperature rise of the measured temperature are as follows:
(1) Raise from 20 ° C to 180 ° C at a temperature rise rate of 10 ° C / min (2) Hold at 180 ° C for 10 minutes, then cool to 0 ° C at a temperature decrease rate of 10 ° C / min (3) Hold at 0 ° C for 10 minutes After that, the temperature was raised to 180 ° C. again at a heating rate of 10 ° C./min. About 5 mg of the resin was precisely weighed, placed in an aluminum pan, and measured once. An empty aluminum pan was used as a reference. At that time, the temperature at the deepest part of the recess of the endothermic peak of the crystalline resin (A) in the temperature raising process (second temperature raising process) of (3) was defined as the temperature Tp indicating the endothermic peak top. When the crystalline resin (A) had two or more endothermic peaks, the temperature showing the highest endothermic peak top among them was defined as Tp.

The weight average molecular weight (Mw) of the resin was measured under the following conditions by dissolving the resin in tetrahydrofuran (THF) and using it as a sample solution by gel permeation chromatography (GPC).
Equipment: HLC-8120 manufactured by Tosoh Corporation
Column: 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μL
Detection device: Refractive index detector Reference material: Tosoh standard polystyrene (TSKstandard POLYSTYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 1900000 355000 1090000 2890000)

The Tg (Tg ₁ ) of the amorphous polyester resin (B) is the method specified in ASTM D3418-82 using DSC (Model Q Series Version 2.8.0.394 manufactured by TA Instruments). ).
The SP value (SP A) of the crystalline resin ( _A ) and the SP value (SP _B ) of the amorphous polyester resin (B) are determined by the method according to Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)].
The acid value and hydroxyl value of the amorphous polyester resin (B) were measured by the method specified in JIS K0070.

The content of molecules having a molecular weight of 1,000 or less in the amorphous polyester resin (B) was determined by data processing the measurement results of each resin by the above GPC as follows.
(1) The holding time at which the molecular weight becomes 1,000 was obtained from the calibration curve centered on the molecular weight and the holding time.
(2) The total peak area (Σ1) was determined.
(3) The peak area (peak area having a molecular weight of 1,000 or less) (Σ2) after the holding time obtained in (1) was obtained.
(4) The content of molecules having a molecular weight of 1,000 or less was determined from the following formula.
Content of molecules with a molecular weight of 1,000 or less (%) = (Σ2) × 100 / (Σ1)
The content (%) of the molecule having a molecular weight of 1,000 or less obtained as described above is described as "the content of the molecule having a molecular weight of 1,000 or less".

Production Example 12
[Crystalline resin (A-1)]
The crystalline segment (a1-1) was used as the crystalline resin (A-1). The Tp of the crystalline resin (A-1) was 60 ° C., and the Mw was 16,000.

Production Example 13
[Synthesis of crystalline resin (A-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 960 parts by weight of the crystalline segment (a1-1) and 40 parts by weight of the segment (a2-1) and 0.5 part by weight of tetrabutoxytitanate as a condensation catalyst. Was reacted at 220 ° C. under a reduced pressure of 0.5 to 2.5 kPa for 4 hours to obtain a crystalline resin (A-2). The acid value of the crystalline resin (A-2) was 1.5 mgKOH / g, the hydroxyl value was 31 mgKOH / g, Tp was 61 ° C., and Mw was 16,500.

Production Example 14
[Synthesis of crystalline resin (A-3)]
In Production Example 13, the same reaction as in Production Example 13 was carried out except that the segments used were changed to 960 parts by weight of the crystalline segment (a1-2) and 40 parts by weight of the segment (a2-2), and the crystalline resin (A). -3) was obtained. The acid value of the crystalline resin (A-3) was 1.7 mgKOH / g, the hydroxyl value was 23 mgKOH / g, Tp was 62 ° C., and Mw was 22,000.

Production Example 15
[Synthesis of crystalline resin (A-4)]
In Production Example 13, the same reaction as in Production Example 13 was carried out except that the segment used was changed to 960 parts by weight of the crystalline segment (a1-3) and 40 parts by weight of the segment (a2-2). A-4) was obtained. The acid value of the crystalline resin (A-4) was 1.5 mgKOH / g, the hydroxyl value was 13 mgKOH / g, Tp was 68 ° C., and Mw was 45,000.

Production Example 16
[Synthesis of crystalline resin (A-5)]
In Production Example 13, the same reaction as in Production Example 13 was carried out except that the segment used was changed to 960 parts by weight of the crystalline segment (a1-4) and 40 parts by weight of the segment (a2-2). A-5) was obtained. The acid value of the crystalline resin (A-5) was 1.3 mgKOH / g, the hydroxyl value was 39 mgKOH / g, Tp was 67 ° C., and Mw was 13,000.

Production Example 17
[Synthesis of crystalline resin (A-6)]
In Production Example 13, the same reaction as in Production Example 13 was carried out except that the segment used was changed to 960 parts by weight of the crystalline segment (a1-5) and 40 parts by weight of the segment (a2-2). A-6) was obtained. The acid value of the crystalline resin (A-6) was 1.6 mgKOH / g, the hydroxyl value was 34 mgKOH / g, Tp was 71 ° C., and Mw was 14,000.

Production Example 18
[Synthesis of crystalline resin (A-7)]
In Production Example 13, the same reaction as in Production Example 13 was carried out except that the segment used was changed to 960 parts by weight of the crystalline segment (a1-6) and 40 parts by weight of the segment (a2-2). A-7) was obtained. The acid value of the crystalline resin (A-7) was 1.7 mgKOH / g, the hydroxyl value was 37 mgKOH / g, Tp was 77 ° C., and Mw was 13,000.

Production Example 19
[Synthesis of crystalline resin (A-8)]
In Production Example 13, the same reaction as in Production Example 13 was carried out except that the segment used was changed to 960 parts by weight of the crystalline segment (a1-7) and 40 parts by weight of the segment (a2-2). A-8) was obtained. The acid value of the crystalline resin (A-8) was 1.3 mgKOH / g, the hydroxyl value was 31 mgKOH / g, Tp was 40 ° C., and Mw was 16,000.

Production Example 20
[Synthesis of crystalline resin (A-9)]
In Production Example 13, the same reaction as in Production Example 13 was carried out except that the segment used was changed to 960 parts by weight of the crystalline segment (a1-8) and 40 parts by weight of the segment (a2-2). A-9) was obtained. The acid value of the crystalline resin (A-9) was 1.5 mgKOH / g, the hydroxyl value was 18 mgKOH / g, Tp was 68 ° C., and Mw was 31,000.

Production Example 21
[Synthesis of crystalline resin (A-10)]
In Production Example 13, the same reaction as in Production Example 13 was carried out except that the segment used was changed to 960 parts by weight of the crystalline segment (a1-9) and 40 parts by weight of the segment (a2-2). A-10) was obtained. The acid value of the crystalline resin (A-10) was 1.4 mgKOH / g, the hydroxyl value was 27 mgKOH / g, Tp was 84 ° C., and Mw was 19,000.

Production Example 22
[Synthesis of crystalline resin (A-11)]
In a reaction vessel equipped with a stirrer and a nitrogen introduction tube, 959 parts by weight of the crystalline segment (a1-9) and 39 parts by weight of the segment (a2-2) were charged and uniformly dissolved at 100 ° C. Further, 2 parts by weight of hexamethylene diisocyanate was charged and reacted at 100 ° C. for 3 hours to obtain a crystalline resin (A-11). The Tp of the crystalline resin (A-11) was 68 ° C., and the Mw was 34000. The crystalline resin (A-11) is a crystalline resin in which the crystalline segment (a12-1) and the segment (a2-2) of the crystalline polyurethane (a12) are chemically bonded. The SP _a10 of the crystalline segment (a12-1) was 9.7 cal / cm ³ ) ^1/2 , the acid value was 1.4 mgKOH / g, the hydroxyl value was 26 mgKOH / g, and the isocyanate content was 1400 ppm.

Comparative manufacturing example 3
[Crystalline resin (A'-1)]
The crystalline segment (a'1-1) was used as the crystalline resin (A'-1). The Tp of the crystalline resin (A'-1) was 61 ° C., and the Mw was 18,000.

Comparative manufacturing example 4
[Synthesis of crystalline resin (A'-2)]
In Production Example 13, the same reaction as in Production Example 13 was carried out except that the segment used was changed to 960 parts by weight of the crystalline segment (a'1-1) and 40 parts by weight of the segment (a2-1), and the crystalline resin was obtained. (A'-2) was obtained. The acid value of the crystalline resin (A'-2) was 1.3 mgKOH / g, the hydroxyl value was 31 mgKOH / g, Tp was 68 ° C., and Mw was 18,500.

Comparative manufacturing example 5
[Synthesis of crystalline resin (A'-3)]
In Production Example 13, the same reaction as in Production Example 13 was carried out except that the segments used were changed to 960 parts by weight of the crystalline segment (a'1-2) and 40 parts by weight of the segment (a2-2). (A'-3) was obtained. The acid value of the crystalline resin (A'-3) was 1.7 mgKOH / g, the hydroxyl value was 22 mgKOH / g, Tp was 66 ° C., and Mw was 25,000.

Table 1 summarizes the analytical values of the crystalline resins (A) and (A') obtained in Production Examples 12 to 21 and Comparative Production Examples 3 to 5.

Production Example 23
[Synthesis of resin (B-1)]
In the reaction vessel, 655 parts by weight of 1.2-propylene glycol, 17 parts by weight of propylene oxide 2 mol addition of bisphenol A, 675 parts by weight of terephthalic acid, 35 parts by weight of adipic acid, 29 parts by weight of benzoic acid, trimellitic acid anhydride. 46 parts by weight and 3 parts by weight of tetrabutoxytitanate were added as a condensation catalyst and reacted at 220 ° C. under pressure, and the reaction was carried out for 10 hours while distilling off the generated water.
Then, the pressure was gradually released and returned to normal pressure, and the reaction was further proceeded under a reduced pressure of 0.5 to 2.5 kPa.
The resin (b-1) was taken out when the flow softening point Tm reached 130 ° C.

In another reaction vessel, 590 parts by weight of 1.2-propylene glycol, 75 parts by weight of propylene oxide 2 mol addition of bisphenol A, 694 parts by weight of terephthalic acid, 79 parts by weight of benzoic acid, 46 parts by weight of anhydrous trimellitic acid, And 3 parts by weight of tetrabutoxytitanate was added as a condensation catalyst, and the reaction was carried out at 220 ° C. under pressure, and the reaction was carried out for 10 hours while distilling off the generated water.
Then, the pressure was gradually released and returned to normal pressure, and the reaction was further proceeded under a reduced pressure of 0.5 to 2.5 kPa. When Tm reached 100 ° C, the pressure was returned to normal and cooled to 180 ° C. After adding 9 parts by weight of trimellitic anhydride and reacting for 1 hour, the resin (b-2) was taken out.

Henschel mixer [FM10B manufactured by Nippon Coke Industries Co., Ltd.] so that the weight ratio (b-1) / (b-2) of the obtained resin (b-1) and resin (b-2) is 50/50. And homogenized to obtain a resin (B-1). The Tg of the resin (B-1) is 61 ° C., Mw is 40,000, the acid value is 5 mgKOH / g, the hydroxyl value is 22 mgKOH / g, the content of molecules having a molecular weight of 1,000 or less is 8.0%, and SP _B. Was 11.9 (cal / cm ³ ) ^1/2 .

Production Example 24
[Synthesis of resin (B-2)]
In the reaction vessel, 365 parts by weight of ethylene oxide 2 mol adduct of bisphenol A, 389 parts by weight of propylene oxide 2 mol adduct of bisphenol A, 285 parts by weight of terephthalic acid, and 3 parts by weight of tetrabutoxytitanate as a condensation catalyst were placed, and nitrogen was added. The reaction was carried out at 220 ° C. with air flow, and the reaction was carried out for 10 hours while distilling off the generated water.
Then, the reaction was carried out under a reduced pressure of 0.5 to 2.5 kPa, the reaction was carried out until the acid value became 2 mgKOH / g or less, and then the mixture was cooled to 180 ° C. After adding 21 parts by weight of trimellitic anhydride and reacting for 1 hour, the resin (b-3) was taken out.

Henschel mixer [FM10B manufactured by Nippon Coke Industries Co., Ltd.] so that the weight ratio (b-1) / (b-3) of the obtained resin (b-1) and the resin (b-3) is 50/50. And homogenized to obtain a resin (B-2). The Tg of the resin (B-2) is 58 ° C., Mw is 35,000, the acid value is 8 mgKOH / g, the hydroxyl value is 36 mgKOH / g, the content of molecules having a molecular weight of 1,000 or less is 9.4%, and SP _B. Was 11.7 (cal / cm ³ ) ^1/2 .

Examples 1 to 11 [Manufacturing of Toner Binders (TB-1) to (TB-11)]
The crystalline resins (A-1) to (A-11), resins (B-1) and (B-2) obtained in the production examples were blended according to the blending ratio (part by weight) in Table 2 to form the present invention. Toner binders for electrophotographic (TB-1) to (T-11) were obtained.

Comparative Examples 1 to 3 [Manufacturing of Toner Binders (TB'-1) to (TB'-3)]
The crystalline resins (A'-1) to (A'-3), resin resins (B-1) and (B-2) obtained in the comparative production example were blended according to the blending ratio (part by weight) in Table 2. , Comparative electrophotographic toner binders (TB'-1) to (TB'-3) were obtained.

Table 2 summarizes the analytical values of the toner binders (TB) and (TB') obtained in Examples 1 to 11 and Comparative Examples 1 to 3.

When the toner binder is heated, cooled, and heated, the endothermic peak area of the crystalline resin (A) in the first temperature raising process measured by DSC is S ₁ , and the crystal in the second temperature raising process. The endothermic peak area of the sex resin (A) was S ₂ , and S ₁ and S ₂ (endothermic peak area at the time of temperature rise) were measured as follows.
About 5 mg of the toner binder was precisely weighed and placed in an aluminum pan, and DSC was measured under the following heating conditions.
Equipment: Q Series Version 2.8.0.394 (manufactured by TA Instruments)
The temperature was raised from 20 ° C. to 10 ° C./min to 180 ° C. (first temperature raising process), then left at 180 ° C. for 10 minutes, and then cooled to 0 ° C. under the condition of 10 ° C./min (No. 1). (1st cooling process), then left at 0 ° C. for 10 minutes, and then heated to 180 ° C. under the condition of 10 ° C./min (second temperature raising process).
DSC was measured from the beginning (20 ° C.) of the first heating process to the end of the second heating process (180 ° C.).
The values of (S ₂ / S ₁ ) × 100 are shown in Table 1. Further, the endothermic heat amount (J / g) of the crystalline resin (A) in the second temperature raising process measured by DSC is shown in Table 1 as “the endothermic heat amount (J) / g derived from (A)”.

The compatibility of the mixture of the crystalline resin (A) and the amorphous polyester resin (B) blended in the proportions shown in Table 2 was evaluated as follows. The results are shown in Table 1.
When the glass transition point (Tg ₁ +30) (° C.) of the amorphous polyester resin (B) is the same as or higher than the temperature Tp (° C.) indicating the heat absorption peak top of the crystalline resin (A) (Tg ₁ +30) ( At the temperature of (° C.), when (Tg ₁ +30) was lower than Tp, it was visually observed whether the whole or a part of the mixture had turbidity at the temperature of Tp.
[Criteria for determining compatibility]
◎: Partially turbid ○: Overall turbidity ×: Transparent

Example 12 [Manufacturing of Toner (T-1)]
Toner binder (TB-1) 100 parts by weight, pigment carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation] 8 parts by weight, charge control agent T-77 [Hodogaya Chemical (manufactured)] 1 part by weight, mold release 4 parts by weight of the agent carnauba wax was premixed using a Henshell mixer [FM10B manufactured by Mitsui Miike Kakoki Co., Ltd.] and then kneaded with a twin-screw kneader [PCM-30 manufactured by Ikekai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher Lab Jet [manufactured by Nippon Pneumatic Industries, Ltd.], the particles are classified by an air flow classifier [MDS-I manufactured by Nippon Pneumatic Industries, Ltd.], and the volume average particle size is increased. Toner particles having a D50 of 7 μm were obtained.
Next, 100 parts by weight of the toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed with a sample mill to obtain the toner (T-1) of the present invention.

<Examples 13 to 21> [Manufacturing of toners (T-2) to (T-11)]
As shown in Table 3, the raw materials were blended to produce toner in the same manner as in Example 12, and toners (T-2) to (T-11) were obtained.

<Comparative Examples 4 to 6> [Manufacturing of Toner (T'-1) to (T'-3)]
As shown in Table 3, the raw materials were blended to produce toner in the same manner as in Example 12, and toners (T'-1) to (T'-3) were obtained.

Table 3 summarizes the evaluation results of the toners (T) and (T') obtained in Examples 11 to 21 and Comparative Examples 4 to 6.

[Evaluation methods]
Low temperature fixability, glossiness, hot offset resistance, fluidity, heat storage stability, charge stability, crushability, image strength, bending resistance, document offset test measurement method, evaluation method, etc. of the toner obtained below. The judgment criteria will be explained.

<Low temperature fixability>
The toner was evenly placed on the paper surface at 0.6 mg / cm ² . At this time, as a method of placing the powder on the paper surface, a printer from which the heat fixing machine was removed was used. Other methods may be used as long as the powder can be uniformly placed at the above weight density.
Measure the low temperature fixing temperature, which is the temperature at which cold offset occurs when this paper is passed through a pressure roller under the conditions of fixing speed (heating roller peripheral speed) 213 mm / sec and fixing pressure (pressurized roller pressure) 10 kg / cm ² . did.
The lower the low temperature fixing temperature, the better the low temperature fixing property. The lower the temperature at which the cold offset occurs, the better the low temperature fixability.

<Glossy>
Fixation evaluation was performed in the same manner as low temperature fixability. A white cardboard was laid under the image, and the glossiness of the printed image was measured at an incident angle of 60 degrees using a gloss meter (“IG-330” manufactured by HORIBA, Ltd.).

[criterion]
⊚: 20 or more ○: 15 or more and less than 20 Δ: 10 or more and less than 15 ×: less than 10

<Hot offset resistance (hot offset generation temperature)>
The fixing was evaluated in the same manner as the low temperature fixing property, and the presence or absence of hot offset to the fixed image was visually evaluated.
The temperature at which the hot offset occurred after passing through the pressure roller was defined as the hot offset resistance (° C).
The higher the temperature at which the hot offset occurs, the better the hot offset resistance.

<Liquidity>
The bulk density (g / 100 mL) of the toner was measured with a powder tester manufactured by Hosokawa Micron, and the fluidity was judged according to the following criteria. Δ or more (30 g / 100 mL or more) is a practical range.

[criterion]
⊚: 36 or more ○: 32 or more and less than 36 △: 27 or more and less than 32 ×: less than 27

<Heat-resistant storage>
After allowing the toner to stand in an atmosphere of 45 ° C. for 24 hours, transfer it to a 42-mesh sieve, shake it with a powder tester manufactured by Hosokawa Micron Co., Ltd. for 10 seconds at a vibration intensity of 5, and remove the toner remaining on the sieve. The weight% was measured and judged according to the following criteria, and the heat-resistant storage stability was evaluated.

[criterion]
Residual toner weight%
◎: 0% by weight or more and less than 15% by weight ○: 15% by weight or more and less than 25% by weight △: 25% by weight or more and less than 30% by weight ×: 30% by weight or more

<Charging stability>
(1) 0.5 g of toner and 20 g of ferrite carrier (F-150, manufactured by Powdertech) were placed in a 50 mL glass bottle, and the humidity was adjusted at 23 ° C. and 50% relative humidity for 8 hours or more.
(2) Friction stir welding was performed at 50 rpm for 10 minutes and 60 minutes with a turbar shaker mixer, and the amount of charge at each time was measured.
A blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used for the measurement.
"Charge amount of friction time 60 minutes / charge amount of friction time 10 minutes" was calculated and used as an index of charge stability.

[criterion]
⊚: 0.8 or more ○: 0.7 or more and less than 0.8 △: 0.6 or more and less than 0.7 ×: less than 0.6

<Crushability>
A coarse crushed product (8.6 mesh pass to 30 mesh-on) that has been kneaded and cooled with a twin-screw kneader is subjected to the following conditions by a supersonic jet crusher LabJet [manufactured by Nippon Pneumatic Mfg. Co., Ltd.]. Finely ground with.
Grinding pressure: 0.5MPa
Crushing time: 10 minutes Adjuster ring: 15 mm
Louver size: Medium Without classifying this, the volume average particle size (μm) was measured with a Coulter counter-TAII (manufactured by Coulter Electronics, USA), and the pulverizability was evaluated according to the following criteria.

[criterion]
⊚: less than 10 ○: 10 or more and less than 11 Δ: 11 or more and less than 12 ×: 12 or more

<Image strength>
A pencil in which the test paper used for measuring the low-temperature fixing temperature (paper obtained by evaluating the low-temperature fixing property, on which the image is fixed) is fixed at an angle of 45 degrees according to JIS K 5600-5-4: 1999. A scratch test was performed by applying a load of 10 g from directly above, and the image strength was evaluated from the scratch-free pencil hardness.
The higher the pencil hardness, the better the image strength. Generally, H or higher is required.

<Bending resistance>
The test paper used for measuring the low temperature fixing temperature was bent so that the image surface was on the inside, and rubbed 5 times with a load of 30 g.
The paper was unfolded and the presence or absence of white streaks after bending on the image was visually determined.
[criterion]
○: No white streaks △: Slightly white streaks ×: White streaks

<Document offset property>
Two sheets of A4 paper on which the image obtained by the evaluation of low temperature fixability was fixed were overlapped with each other on the fixed surfaces, weighted by 420 g (0.68 g / cm ² ), and allowed to stand at 65 ° C. for 10 minutes. ..
The document offset property was evaluated according to the following criteria for the state when the overlapped papers were pulled apart.

[criterion]
○: No resistance △: There is a crisp sound, but the image does not peel off from the paper surface ×: The image peels off from the paper surface

The above evaluation results are shown in Table 3.

As is clear from the evaluation results in Table 3, all the toners of the toners of the present invention (Examples 11 to 21) using the toner binders of the present invention (Examples 1 to 11) were excellent in performance evaluation. Results were obtained. On the other hand, some performance items of the comparative toners (Comparative Examples 4 to 6) using the comparative toner binders (Comparative Examples 1 to 3) were defective.

The toner binder and toner of the present invention are excellent in toner fluidity, heat storage stability, charge stability, crushability, image strength and bending resistance, while achieving both low temperature fixability, glossiness and hot offset resistance. It is useful as a toner for static charge image development used in electrophotographic, electrostatic recording, electrostatic printing, and the like.

Claims (13)

A toner binder containing a crystalline resin (A) which is a polycondensate of an alcohol component (x) and a carboxylic acid component (y), wherein the alcohol component (x) is a linear or branched product having 2 to 12 carbon atoms. It contains at least two types of aliphatic diols (x1), and the molar mass of the component (x1a) having the largest number of moles in (x1) and the molar of any one of the components other than (x1a) (x1b). The difference in molar mass of at least one of the combinations with mass is less than 15, and the total content of the components (x1b) other than (x1a) in (x1) is the alcohol excluding the end-capping agent (a2). It is 0.05 to 3 mol% based on the total number of moles of the component (x), and is in the range of 40 ° C. to 100 ° C. when the temperature is raised from 30 ° C. to 10 ° C./min. Toner binder having at least one heat absorption peak top in the chart by. The content of the component (x1a) having the largest number of moles in (x1) is 90 to 99 based on the total number of moles of the alcohol component (x) excluding the end-capping agent (a2) . It is 95 mol%, and the total content of the diol component (x2) other than the above (x1) and the alcohol component (x3) having a trivalent or higher value is the total molar amount of the alcohol component (x) excluding the end-capping agent (a2). The toner binder according to claim 1 , which is 9.5 mol% or less based on the number . The toner binder according to claim 1 or 2, wherein the carboxylic acid component (y) contains an aliphatic dicarboxylic acid having 4 to 12 carbon atoms. The toner binder according to any one of claims 1 to 3, wherein the crystalline resin (A) is a resin satisfying the following relational expression (1).
35 ≦ (S ₂ / S ₁ ) × 100 ≦ 100 (1)
[However, in the chart by the differential scanning calorimeter (DSC), the endothermic peak of the first endothermic process when the temperature of the toner binder is raised from 30 ° C to 10 ° C / min to 180 ° C is S. ₁ (J / g) The endothermic peak of the second endothermic process when the temperature is raised to 180 ° C under the condition of 10 ° C / min after cooling to 0 ° C under the condition of 10 ° C / min is S. ₂ (J / g). ] The toner binder according to claim 4, wherein the endothermic peak in the second temperature raising process has an endothermic amount of 1 to 30 J / g. The toner binder according to any one of claims 1 to 5, wherein the crystalline resin (A) has at least one group selected from the group consisting of a urethane group and a urea group. The toner binder according to any one of claims 1 to 6, further comprising an amorphous polyester resin (B) which is a polycondensate of an alcohol component (x) and a carboxylic acid component (y). The toner binder according to claim 7, wherein the weight ratio (B / A) of the amorphous polyester resin (B) to the crystalline resin (A) is 50/50 to 97/3. When the glass transition point Tg ₁ +30 (° C.) of the amorphous polyester resin (B) is the same as or higher than the temperature Tp (° C.) indicating the heat absorption peak top of the crystalline resin (A), the temperature is (Tg ₁ +30). The toner binder according to claim 7 or 8, wherein (Tg ₁ +30) is turbid in whole or a part of the toner binder at the temperature of Tp when it is lower than Tp. The crystalline segment (a1) in which the crystalline resin (A) is compatible with the amorphous polyester resin (B) and the end sealant (a2) incompatible with the amorphous polyester resin (B). The toner binder according to any one of claims 7 to 9, wherein the resin is chemically bonded to the resin. The toner binder according to claim 10, wherein the segment (a1) and the end-capping agent (a2) satisfy both the following relational expressions (2) and (3).
｜ SP _a1 -SP _B ｜ ≦ 2.0 (cal / cm ³ ) ^1/2 (2)
｜ SP _a2 -SP _B ｜ ≧ 2.0 (cal / cm ³ ) ^1/2 (3)
[However, SP _a1 indicates the SP value of the segment (a1), SP _a2 indicates the SP value of the end sealant (a2), and SP _B indicates the SP value of the amorphous polyester resin (B). ] Claims 7 to 11 where the amorphous polyester resin (B) is a resin in which the peak area having a molecular weight of 1,000 or less is 10% or less of the total peak area in a chromatogram whose molecular weight is measured by gel permeation chromatography. One of the toner binders described. A toner containing the toner binder and the colorant according to any one of claims 1 to 12.